CN107243354A - Reduce light-off temperature and SO2Oxygenation efficiency honeycomb type flue gas denitration catalyst and preparation method thereof - Google Patents
Reduce light-off temperature and SO2Oxygenation efficiency honeycomb type flue gas denitration catalyst and preparation method thereof Download PDFInfo
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- CN107243354A CN107243354A CN201710436266.4A CN201710436266A CN107243354A CN 107243354 A CN107243354 A CN 107243354A CN 201710436266 A CN201710436266 A CN 201710436266A CN 107243354 A CN107243354 A CN 107243354A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- 239000003546 flue gas Substances 0.000 title claims abstract description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 47
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000006213 oxygenation reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 22
- 239000011733 molybdenum Substances 0.000 claims abstract description 20
- 239000003365 glass fiber Substances 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 43
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- 239000006210 lotion Substances 0.000 claims description 11
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000033228 biological regulation Effects 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 47
- 238000006722 reduction reaction Methods 0.000 description 25
- 239000002245 particle Substances 0.000 description 21
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 description 16
- 238000004523 catalytic cracking Methods 0.000 description 15
- 229910001385 heavy metal Inorganic materials 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 14
- 229940010552 ammonium molybdate Drugs 0.000 description 14
- 235000018660 ammonium molybdate Nutrition 0.000 description 14
- 239000011609 ammonium molybdate Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000007493 shaping process Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000002002 slurry Substances 0.000 description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 11
- 239000003500 flue dust Substances 0.000 description 11
- 230000001413 cellular effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 235000021355 Stearic acid Nutrition 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 235000010980 cellulose Nutrition 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- -1 hydroxypropyl Chemical group 0.000 description 4
- 210000001161 mammalian embryo Anatomy 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- CLIMUTTYEDYWND-UHFFFAOYSA-N [Mo](=O)(=O)=O.[O-2].[Ti+4].[O-2] Chemical compound [Mo](=O)(=O)=O.[O-2].[Ti+4].[O-2] CLIMUTTYEDYWND-UHFFFAOYSA-N 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000005360 mashing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B01J35/613—
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
One kind reduction light-off temperature and SO2Oxygenation efficiency honeycomb type flue gas denitration catalyst, comprises the following steps：Titanium source presoma is dissolved in acid and forms solution；Molybdenum source presoma and phosphorus source precursor are dissolved and to form solution；Above solution is well mixed, regulation pH value to 7~12 is precipitated, filtering then adds deionized water, vanadium source precursor solution, after being well mixed, is directly dried, is calcined, grind to form powder；Extrusion aid, solution, the pore creating material of the formation of molybdenum source presoma are added in powder, paste is added water into while stirring, add nano silicon, glass fibre, binding agent, uniform mixing, honeycomb fashion idiosome is extruded using extruder, dried idiosome is first placed in silicon source precursor solution again and impregnated, is got product after roasting.To overcome in the prior art, denitrating catalyst activated centre in flue gas is unbalanced, SO2The defect that oxygenation efficiency is high, anti-Poisoning is poor.
Description
Technical field
The present invention relates to one kind reduction light-off temperature and SO2Oxygenation efficiency honeycomb type flue gas denitration catalyst and its preparation side
Method, especially a kind of to resist uneven denitrating catalyst of heavy metals of flue gases deposition and preparation method thereof, the invention belongs to nothing
Machine new material technology field.
Background technology
Nitrogen oxides (NOx) it is one of main atmosphere pollution, emission request is increasingly strict.China《" 12 " are saved
Can the comprehensive programme of work of emission reduction》Middle regulation：By 2015, national discharged nitrous oxides total amount declined 10% than 2010.
The GB13223-2001 that the national environmental protection of in September, 2011 portion is promulgated《Fossil-fuel power plant atmospheric pollutant emission standard》Thermal power plant NOx is arranged
Put concentration and make more strict requirements：Newly-built the 3rd period, enlarging, the coal-burning boiler of reconstruction are provided, NOx highests allow discharge
Concentration is 100mg/m3.What national environmental protection portion was promulgated《Petroleum refining industry pollutant emission standard》It is required that：On July 1st, 2015
Rise, nitrogen oxides requirement is less than 200mg/m in newly-built catalytic cracking unit discharge regenerated flue gas3, special emission limit requires small
In 100mg/m3, on July 1st, 2017, existing enterprise also performed the standard.In numerous gas denitrifying technologies, selective catalysis is also
The technology that it is still international mainstream that former method (Selective Catalytic Reduction, SCR), which is, its NOxRemoval efficiency is reachable
To 80%~90%.Wherein, denitrating catalyst is the core of SCR technology, and developed country just have developed in the eighties in last century
For a series of denitrating catalysts of coal characteristics, boiler type etc., many R＆D institutions of China are coal-fired for China with enterprise
Boiler and catalytic cracking flue gas situation have also carried out a series of research, and develop some denitrating catalysts.
CN201010537130 proposes the method that denitrating catalyst is prepared using hydrothermal method, first by titanium source presoma
With the mixing of molybdenum source presoma, it is placed in autoclave and carries out hydro-thermal reaction, be filtered, washed and dried and obtain titanium molybdenum powder denitration catalyst
Agent, while can also introduce the elements such as vanadium and molybdenum, prepares multi-metal-oxide catalyst.Catalyst activity component prepared by this method
Crystal grain is small, specific surface area is larger, but by being sufficiently mixed process material aggregation extent of the same race may be caused higher due to no
Phenomenon occurs, and certain influence is had on catalyst activity.
CN201110345605 proposes a kind of preparation method of denitrating catalyst, and molybdenum is sequentially added into metatitanic acid slurry
Sour ammonium, ammonium molybdate and ammonium metavanadate, ultrasonic wave mashing, then pH value is adjusted to 4.0~6.5, stand, separate, drying is catalyzed
Agent powder.This method technique is simple, cost is low, but ammonium metavanadate is added with solid, and the dissolubility of vanadium is still to be tested, and vanadium disperses
Although activity very high, SO when uneven2/SO3Conversion ratio can be higher, influences catalyst performance.
CN201210400949 proposes a kind of preparation method of titanium dioxide-molybdenum trioxide composite granule, by para-molybdic acid
Ammonium salt solution is added in metatitanic acid slurries, and directly vacuum drying obtains finished product after stirring.This method technique is simple, but titanium-molybdenum
Mixing intensity is relatively low, and the performance to material can have a certain impact.
CN103143396B proposes a kind of preparation method of honeycomb type denitrification catalyst, by titanium dioxide, silica,
Active material and into paste, then adding additives, glass etc., last extrusion molding.This method technique is simple, but active material
Distribution it is bad, cause the denitration efficiency of catalyst relatively low.
In summary, the preparation of denitrating catalyst is directed to the mixing of Multimetal oxide, hybrid mode and preparation work
The difference of skill can not distinguish the denitration performance of catalyst, powder catalyst n O completelyxConversion ratio can reach more than 90%, and
Preformed catalyst activity has certain decline, and on the one hand the catalytic activity of explanation special metal oxide is higher, and scattered inequality is still
Higher NO can be obtainedxConversion ratio；On the other hand, shaping of catalyst process also results in catalyst activity reduction.Meanwhile, urge
The quality of agent overall performance also needs to be verified that the preparation of catalyst will also take into account industrial amplification from otherwise sign
The factor such as operability.
The content of the invention
It is a primary object of the present invention to provide a kind of reduction light-off temperature and SO2Oxygenation efficiency honeycomb fashion flue gas denitration catalyst
Agent and preparation method thereof, to overcome in the prior art, denitrating catalyst activated centre in flue gas is unbalanced, SO2Oxygenation efficiency
High, anti-Poisoning is poor and active unstable defect.
The object of the present invention is achieved like this, one kind reduction light-off temperature and SO2Oxygenation efficiency honeycomb fashion denitrating flue gas is urged
Agent, the method for preparing catalyst comprises the following steps：
(1) titanium source presoma is dissolved in acid and forms solution；
(2) molybdenum source presoma and phosphorus source precursor are dissolved to form solution, and are well mixed with the solution of (1)；
(3) well mixed rear solution ph, to 7~12, is precipitated obtained by regulating step (2), and filter cake is washed to obtain in filtering；
(4) deionized water is added in filter cake obtained by step (3), is tuned into pulpous state, add vanadium source precursor solution, mixing is equal
After even, directly it is dried, is calcined, grinds to form powder；
(5) extrusion aid, solution, the pore creating material of the formation of molybdenum source presoma are added in powder obtained by step (4), while stirring
Paste is added water into, and adjusts pH value to 7~12；
(6) nano silicon, glass fibre, binding agent are added in lotion obtained by step (5), stir mixing,
Honeycomb fashion idiosome is extruded using extruder；
(7) dry gained idiosome in step (6), then be placed in dipping in silicon source precursor solution, got product after roasting.
Titanium source presoma, molybdenum source presoma, vanadium source presoma, phosphorus source precursor, silicon source presoma, pore-creating in the present invention
Agent, binding agent, extrusion aid use the conventional material of denitrating catalyst preparation in the prior art, and consumption is also according to technique
Feature selects appropriate amount, and the present invention is not any limitation as especially.The present invention also recommended preferred scheme.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably titanyl sulfate or metatitanic acid to state titanium source presoma in step (1), and the acid is preferably inorganic acid, the solution of formation with
TiO2Meter, content is preferably 15~40g/L.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably metamolybdic acid ammonium or ammonium molybdate to state molybdenum source presoma in step (2), and the molybdenum source presoma is with MoO3Meter, titanium source presoma
With TiO2Meter, it is well mixed obtained by step (2) after Molybdenum in Solution source presoma and titanium source presoma mass ratio be preferably 2.0~
5.0:100.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably 0.5~2 to state molybdenum source presoma used and titanium source forerunner's body mass ratio used in step (1) in step (5):100.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably one kind or several in phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and triammonium phosphate to state phosphorus source presoma in step (2)
Kind, phosphorus source presoma is with P2O5Meter, titanium source presoma is with TiO2In meter, well mixed rear solution obtained by step (2) before phosphorus source
The mass ratio for driving body and titanium source presoma is preferably 0.1~1.5:100；
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
The mode being well mixed in step (2) and step (4) is stated using stirring, the time is 0.5~3h.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
State regulation pH value medicament in step (3) be preferably after ammoniacal liquor, regulation pH value be more than 9.0.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
State and powder is ground to form in step (4), best 0.01~50 μm of powder granule particle diameter.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably 10~60min to state mixing time in step (5).
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably 30~360min to state mixing time in step (6).
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is stearic acid or glycerine to state in step (5) extrusion aid, addition with TiO2The mass ratio difference of the titanium source presoma of meter is best
For 0.01~1.0:100.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably the one or more in polyethylene glycol oxide, polymethyl methacrylate, sesbania powder to state pore creating material in step (5), is added
Measure and with TiO2The mass ratio of the titanium source presoma of meter is preferably 0.01~1.0 respectively:100.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
Vanadium source presoma is stated with V2O5Meter, the titanium source presoma is with TiO2The matter of meter, vanadium source presoma consumption and titanium source presoma consumption
Measure ratio preferably 0.3~2.0:100.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably 35~55% to state slurry water quality content in step (4).
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
It is preferably 25~40% to state paste water quality content in step (5).
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
State in step (6) nano silicon, glass fibre, binding agent addition with TiO2The quality score of the titanium source presoma of meter
Hao Wei 0.1~2.5:100,1~8:100,0.1~1.0:100, wherein binding agent is preferably carboxymethyl cellulose or hydroxypropyl
One or both of base cellulose.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
State water or alcoholic solution that silicon source precursor solution in step (7) is tetraethyl orthosilicate, wherein tetraethyl orthosilicate mass content most
It is well 3~15%, dip time is preferably 5~20s.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, institute
The hole count for stating extrusion honeycomb fashion idiosome section in step (6) is preferably 3 × 3 holes to 40 × 40 holes, preferably 15 × 15 holes, 18 × 18
Hole, 20 × 20 holes, 21 × 21 holes, 22 × 22 holes, 25 × 25 holes, 30 × 30 holes.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, its
It is characterised by, highest sintering temperature is preferably 400~650 DEG C in the step (4) and step (7), and roasting time is best
For 4~40h.
Reduction light-off temperature and SO of the present invention2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, its
It is characterised by, the inorganic acid is sulfuric acid or nitric acid.
The acting as of binding agent of the present invention is bonded other materials, lotion is formed, beneficial to shaping of catalyst.
Pore creating material of the present invention, leaves in catalyst matrix micro- by the use of its own molecular structure as template, after roasting
Hole, increases the microcellular structure of catalyst.
Extrusion aid of the present invention, using its lubrication to catalyst substrates, improved catalysts extrusion molding performance,
Molding materials are made not glue wall.
Present invention also offers above-mentioned reduction light-off temperature and SO2The preparation side of oxygenation efficiency honeycomb type flue gas denitration catalyst
Catalyst prepared by method, the catalyst is vanadium system O composite metallic oxide catalyst, and its physical index and composition are preferably：Compare table
40~120m of area2/ g, by weight percentage, wherein being 80~90% containing titanium dioxide, containing molybdenum trioxide 1~10%, contains
Vanadic anhydride 0.3~3%, containing phosphorus pentoxide 0.1%~2%, containing silica 0.1%~5%, containing alundum (Al2O3)
0.1%~10%.
Beneficial effects of the present invention：
(1) using the method for mixing in situ, titanium atom and molybdenum atom is mixed in atomic level, cause follow-up co-precipitation
During the crystal that produces, lattice defect is more, and mixed-metal oxides particle diameter is small and homogeneous, bigger than surface, improves simultaneously
Turn brilliant temperature of titanium dioxide crystal, beneficial to the performance of catalytic activity；
(2) vanadium source is added when titanium dioxide-molybdenum trioxide co-precipitation material is not calcined, in titanium-tungsten particle surface penetration
It is deeper, connect closer, disperse evenly, fired rear catalyst activity is more stable；
(3) using phosphorous oxides in the deposition of catalyst microparticle surfaces, increase catalyst surface acidity improves catalyst
Low temperature active.
(4) the vanadium molybdenum titanium phosphorus powder material prepared entered after roasting, and covered one layer of molybdenum trioxide on its surface, while plus
Enter pore-creating auxiliary agent, also possessed nanometer level microporous while making catalyst particle surface that there are more molybdenum oxides to adhere to, both can be with
Heavy metals of flue gases oxide is resisted in its surface nonuniform deposition, high catalyst performance can be ensured again.
(5) gap of titanium dioxide matrix particle is filled using nanometer silicon dioxide particle, increases the cause of catalyst matrix
Density, and then increase the intensity of calcined catalyst.
(6) using pore creating material, binding agent, the auxiliary agent such as glass fibre by catalyst preparation into excellent activity and intensity
Cellular catalyst, beneficial to its modularization assembling and the long-period stable operation on industrial denitrification apparatus.
(7) non-calcined catalyst idiosome is impregnated using silicon source precursor solution, calcined catalyst surface can be attached
One layer of porous, inorganic silicon, the water repelling property of catalyst can be increased, while sulfur dioxide in flue gas contact can also be hindered to urge
The activated centre of agent layer, reduces SO2Oxygenation efficiency.
(8) use baking modes to be calcined for echelon, can so make moisture and organic principle in catalyst matrix etc. by
Step release, reduces the stress concentration in catalyst roasting process, increases yield rate.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The experimental method of unreceipted actual conditions in example, generally according to normal condition.
Titanium source precursor solution：
In the present invention, solution is formed in titanium source presoma vitriolization, there is no particular restriction to titanium source presoma, generally limit
It is set in titanyl sulfate or metatitanic acid, titanium source precursor solution with TiO2Meter, titanium source presoma content is 15~40g/L.If small
In 15g/L, then solution is too dilute, and the combination of other materials is more loose, and production efficiency is relatively low；If more than 40g/L, due to dense
Du Taigao and reduced with the mixing intensities of other materials, cause fusion bad.
Each material proportion in denitrating catalyst：
In the present invention, denitrating catalyst mainly includes titanium source presoma, molybdenum source presoma, phosphorus source presoma, vanadium source forerunner
Body, pore creating material, binding agent etc., if molybdenum source presoma is less, can influence the scattered and catalyst activity of main active material stable
Property, cause catalyst performance poor；If without phosphorus source presoma, the light-off temperature of catalyst can be influenceed；If pore-creating dosage is more,
Molybdenum trioxide can be influenceed in the absorption of catalyst particle surface, catalyst porosity is influenceed if very little；Binding agent is less, can shadow
Shaping of catalyst is rung, shaping of catalyst intensity is then influenceed too much；Glass fibre can make catalyst be difficult to be molded too much, then make very little
Catalyst strength is reduced.
Preformed catalyst sample and dust (can be the dust of catalytic cracking flue gas dust or other flues) in flue
Hybrid technique：In air atmosphere, at 240 DEG C, circulation is passed through 40~60 mesh in flue in the fresh catalyst duct of preparation
Heavy metallic oxide content about 1% in dust 24h, catalytic cracking chimney flue dust, takes out catalyst and is evaluated afterwards.It is fresh to urge
Heavy metal in dust with that in flue dust contact process, can be transferred on fresh catalyst, cause fresh catalyst by agent
Surface-active declines, and reduces denitrating catalyst overall performance.
Stationary state NOxConversion ratio appreciation condition：Air speed 5000h-1, 240 DEG C of reaction temperature, air inlet NOxFor 400mg/Nm3、SO2
For 200mg/Nm3, ammonia nitrogen ratio be that 1, water content is 5%.
SCR denitration reacts light-off temperature appreciation condition：Air speed 5000h-1, 130~300 DEG C of reaction temperature, air inlet NOxFor
400mg/Nm3、SO2For 200mg/Nm3, ammonia nitrogen ratio be that 1, water content is 5%.Denitration rate be more than 80% when reaction temperature be
Temperature living.
NOx、SO2Method for measurement of concentration：Flue gas continuous on-line analysis instrument, Siemens ULTRAMAT23.
The escaping of ammonia assay method：Public places sanitary method of inspection part 2：Chemical pollutant (GBT 18204.2-
2014) indigo spectrophotometry specified in.Change ammonia nitrogen ratio, control outlet NOxConcentration is in 40~50mg/Nm3When measure ammonia
Escape.
SO2/SO3Conversion ratio assay method：Wet desulfurization of flue gas by limestone-gypsum method device performance acceptance test specification (DL/
T998-2006)。
Following examples are that the present invention is illustrated, and " % " described in embodiment and comparative example refers to quality percentage and contained
Amount.
Embodiment 1：
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Count 22.5g molybdic acid
Ammonium, with P2O54.5g phosphoric acid solution is counted, is formed and contains TiO2For 35g/L mixed solutions, stir and ammoniacal liquor regulation pH is gradually added after 2h
Value is to 9.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again,
Add with V2O512.5g ammonium metavanadate solution is counted, 1.5h is stirred, dries, 8h is calcined at 550 DEG C, then grind to form particle diameter less than 20
μm powder；Powder again with MoO3Meter 7.5g ammonium molybdate, 4g stearic acid, 3g polyethylene glycol oxides and deionized water is made aqueous
30% lotion, adjusts pH value to 8.5 with ammoniacal liquor, 5g nano silicons, 17.5g glass fibres, 4g carboxylic first is added after stirring
Base cellulose, stirring 40min, sealing and standing 24h, utilizes the hole cellular catalyst idiosome of extruder for shaping 6 × 6 afterwards；
Honeycomb fashion denitration catalyst is obtained after 15s in the ethanol solution containing tetraethyl orthosilicate 10%, 550 DEG C of roasting 8h are inserted after idiosome drying
Agent.Above-mentioned gained fresh catalyst is evaluated respectively after being contacted with catalytic cracking flue dust containing heavy metal, the results are shown in Table 1 data.
Comparative example 1：
Phosphoric acid solution is added without, remaining is same as Example 1, will contained with TiO2Meter 500g titanyl sulfate is dissolved in sulphur
In acid solution, add and contain with MoO322.5g ammonium molybdate solution is counted, is formed and contains TiO2For 35g/L mixed solutions, after stirring 2h by
Step adds ammoniacal liquor and adjusts pH value to 9.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into aqueous again
Rate is 50% slurry, is added with V2O512.5g ammonium metavanadate solution is counted, 1.5h is stirred, dries, be calcined 8h at 550 DEG C, then
Grind to form less than 20 μm powders of particle diameter；Powder again with MoO3Count 7.5g ammonium molybdate, 4g stearic acid, 3g polyethylene glycol oxides and go
Ion water making adjusts pH value to 8.5 with ammoniacal liquor, 5g nano silicons, 17.5g glass is added after stirring into aqueous 30% lotion
Glass fiber, 4g carboxymethyl celluloses, stirring 40min, sealing and standing 24h, utilize the hole honeycomb of extruder for shaping 6 × 6 afterwards
Formula catalyst idiosome；Obtained after 15s in the ethanol solution containing tetraethyl orthosilicate 10%, 550 DEG C of roasting 8h are inserted after idiosome drying
Honeycomb type denitrification catalyst.Above-mentioned gained fresh catalyst with being evaluated respectively after catalytic cracking flue dust containing heavy metal high temperature contact,
It the results are shown in Table 1 data.
Embodiment 2
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Count 22.5g molybdic acid
Ammonium, with P2O54.0g phosphoric acid solution is counted, is formed and contains TiO2For 30g/L mixed solutions, stir and ammoniacal liquor regulation is gradually added after 1.5h
PH value is to 10, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again,
Add with V2O510g ammonium metavanadate solution is counted, 1.5h is stirred, dries, 8h is calcined at 550 DEG C, then grind to form particle diameter less than 30 μm
Powder；Powder again with MoO3Meter 7.5g ammonium molybdate, 3.5g stearic acid, 3.5g polyethylene glycol oxides and deionized water is made aqueous
32% lotion, adjusts pH value to 8.0 with ammoniacal liquor, 4.5g nano silicons, 17.5g glass fibres, 4g carboxylics is added after stirring
Methylcellulose, stirring 40min, sealing and standing 24h, utilizes the hole cellular catalyst embryo of extruder for shaping 5 × 5 afterwards
Body；10s in the ethanol solution containing tetraethyl orthosilicate 5% is inserted after idiosome drying, honeycomb fashion denitration is obtained after 550 DEG C of roasting 8h and urges
Agent.Above-mentioned gained fresh catalyst is evaluated respectively after being contacted with catalytic cracking flue dust containing heavy metal, the results are shown in Table 1 data.
Comparative example 2
Impregnated not in the ethanol solution of tetraethyl orthosilicate, remaining is same as Example 2, will contain with TiO2Count 500g's
Titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Count 22.5g ammonium molybdate, with P2O5Count 4.0g phosphoric acid solution, shape
Into containing TiO2For 30g/L mixed solutions, stir and ammoniacal liquor regulation pH value is gradually added after 1.5h to 10, after precipitation is complete, filters, wash
Wash；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, added with V2O5The ammonium metavanadate for counting 10g is molten
Liquid, stirs 1.5h, dries, 8h is calcined at 550 DEG C, then grind to form less than 30 μm powders of particle diameter；Powder again with MoO3Count 7.5g
Ammonium molybdate, 3.5g stearic acid, 3.5g polyethylene glycol oxides and deionized water be made aqueous 32% lotion, with ammoniacal liquor adjust pH value
To 8.0, Ludox (final dioxide-containing silica is same as Example 2), 17.5g glass fibres, 4g carboxymethyls are added after stirring
Cellulose, stirring 40min, sealing and standing 24h, utilizes the hole cellular catalyst idiosome of extruder for shaping 5 × 5 afterwards；Embryo
After body drying, honeycomb type denitrification catalyst is obtained after 550 DEG C of roasting 8h.Above-mentioned gained fresh catalyst is with catalytic cracking containing a huge sum of money
Evaluated respectively after category flue dust contact, the results are shown in Table 1 data.
Embodiment 3
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Meter 20g ammonium molybdate,
With P2O53.5g phosphoric acid solution is counted, is formed and contains TiO2For 30g/L mixed solutions, stir and ammoniacal liquor regulation pH is gradually added after 1.0h
Value is to 9, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 45% again, plus
Enter with V2O59g ammonium metavanadate solution is counted, 1.0h is stirred, dries, 8h is calcined at 550 DEG C, then grind to form less than 15 μm powder of particle diameter
Body；Powder again with MoO3Meter 5g ammonium molybdate, 3.0g stearic acid, 3.0g polyethylene glycol oxides and deionized water is made aqueous 28%
Lotion, adjust pH value to 8.2 with ammoniacal liquor, 3.5g nano silicons, 22.5g glass fibres, 3g carboxymethyls added after stirring
Cellulose, stirring 40min, sealing and standing 24h, utilizes the hole cellular catalyst idiosome of extruder for shaping 20 × 20 afterwards；
Honeycomb fashion denitration catalyst is obtained after 6s in the ethanol solution containing tetraethyl orthosilicate 8%, 550 DEG C of roasting 8h are inserted after idiosome drying
Agent.Above-mentioned gained fresh catalyst is evaluated respectively after being contacted with catalytic cracking flue dust containing heavy metal, the results are shown in Table 1 data.
Comparative example 3
Technique used presses CN201110345605 embodiments 1, by the metatitanic acid scattered mashing of dust technology, filters to neutrality,
Add water metatitanic acid mashing is scattered, obtained metatitanic acid slurry.Ammonium tungstate, ammonium phosphate, molybdenum are sequentially added in metatitanic acid slurry
Sour ammonium and ammonium vanadate, make the mass ratio of four kinds of ammonium salts and metatitanic acid reach the situation of embodiment 3, make its composition identical, then will
Mixed material allows the ammonium salt of addition to dissolve with stirring to pulp, disperseed, and ammonium salt is fully adsorbed to metatitanic acid surface, is adjusted with nitric acid
PH value is saved to 5.0.Stand, dry, 300 DEG C of heat treatment 4h are to obtain catalyst powder.Grind powder granulating footpath and be less than 15 μm of powder
Body, then be made with 3.0g stearic acid, 3.0g polyethylene glycol oxides and deionized water aqueous 28% lotion, with ammoniacal liquor adjust pH value to
8.2,3.5g nano silicons, 22.5g glass fibres, 3g carboxymethyl celluloses are added after stirring, stirring 40min, sealing are quiet
24h is put, the hole cellular catalyst idiosome of extruder for shaping 20 × 20 is utilized afterwards；After idiosome drying, after 550 DEG C of roasting 8h
Obtain honeycomb type denitrification catalyst.Above-mentioned gained fresh catalyst is evaluated respectively after being contacted with catalytic cracking flue dust containing heavy metal,
It the results are shown in Table 1 data.
Embodiment 4
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Meter 15g ammonium molybdate,
With P2O55.5g phosphoric acid solution is counted, is formed and contains TiO2For 30g/L mixed solutions, stir and ammoniacal liquor regulation pH is gradually added after 1.0h
Value is to 10.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 40% again,
Add with V2O58g ammonium metavanadate solution is counted, 1.0h is stirred, dries, 8h is calcined at 550 DEG C, then grind to form particle diameter less than 10 μm
Powder；Powder again with MoO3Meter 3.5g ammonium molybdate, 3.0g stearic acid, 3.5g polyethylene glycol oxides and deionized water is made aqueous
32% lotion, adjusts pH value to 8.2 with ammoniacal liquor, 2.5g nano silicons, 15g glass fibres, 3.5g carboxylics is added after stirring
Methylcellulose, stirring 40min, sealing and standing 24h, utilizes the hole cellular catalyst embryo of extruder for shaping 18 × 18 afterwards
Body；5s in the ethanol solution containing tetraethyl orthosilicate 13% is inserted after idiosome drying, and obtaining honeycomb fashion denitration after 550 DEG C of roasting 8h urges
Agent.Above-mentioned gained fresh catalyst is evaluated respectively after being contacted with catalytic cracking flue dust containing heavy metal, the results are shown in Table 1 data.
Comparative example 4
Technique used presses CN103143396 embodiments 1, a kind of honeycomb type flue gas denitration catalyst, with the raw material of parts by weight
18 × 18 hole cellular catalysts of extruded shaping, sintering are formed：Nano titanium oxide, nano silicon, ammonium phosphate, molybdic acid
Ammonium, ammonium metavanadate, glass fibre, extrusion aid, cellulose, polyethylene glycol oxide, sesbania powder.Catalyst activity formula reaches embodiment
4 situations, make its composition identical.Above-mentioned gained fresh catalyst and after being mixed with catalytic cracking vanadium-containing wasting catalyst (LDR series)
Catalyst is evaluated respectively, the results are shown in Table 1 data.
Embodiment 5：
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with MoO3Meter 10g ammonium molybdate,
With P2O53.5g phosphoric acid solution is counted, is formed and contains TiO2For 35g/L mixed solutions, stir and ammoniacal liquor regulation pH value is gradually added after 2h
To 9.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, plus
Enter with V2O55g ammonium metavanadate solution is counted, 1.5h is stirred, dries, 8h is calcined at 550 DEG C, then grind to form less than 20 μm powder of particle diameter
Body；Powder again with MoO3Meter 2.5g ammonium molybdate, 4g glycerine, 3g polymethyl methacrylates and deionized water is made aqueous
30% lotion, adjusts pH value to 8.5 with ammoniacal liquor, 4g nano silicons, 17.5g glass fibres, 4g hydroxypropyls is added after stirring
Base cellulose, stirring 40min, sealing and standing 24h, utilizes the hole cellular catalyst embryo of extruder for shaping 25 × 25 afterwards
Body；15s in the ethanol solution containing tetraethyl orthosilicate 3% is inserted after idiosome drying, and obtaining honeycomb fashion denitration after 550 DEG C of roasting 8h urges
Agent.Above-mentioned gained fresh catalyst the results are shown in Table 1 number with being evaluated respectively after catalytic cracking flue dust containing heavy metal high temperature contact
According to.
The embodiment of table 1 and comparative example evaluating data contrast table
Found by embodiment and comparative example：The denitrating catalyst of the resistance heavy metal deposition of embodiment has good effect
Really, it is preliminary the mixing rank of active material is reached molecule rank by mixing in situ, through being co-precipitated the nanometer slightly evacuated
Particle, then barium oxide is introduced in particle surface and shallow-layer, catalyst intermediate is obtained after roasting, is ground to form after powder, is being made
Strengthen the co-catalyst for being introduced into and hindering that heavy metallic oxide is deposited in gas phase in the presence of the agent of hole again, in nano silicon, glue
Tie NO in formed honeycomb shape denitrating catalyst under the auxiliary of material such as agent, evaluating catalystxConversion ratio ammonia nitrogen ratio be 1 when,
Up to more than 98%, and the light-off temperature of catalyst is relatively low, through with after catalytic cracking mixed processing containing heavy metal dusts, the escaping of ammonia
Almost do not increase, catalyst performance is excellent；In denitrating catalyst preparation method, if being handled without (5) step, only retain first
Vanadium molybdenum titanium phosphorus catalyst sample after secondary roasting, after catalytic cracking flue dust containing heavy metal mixed processing, catalytic activity slightly lowers；If
There is no silicon source presoma impregnation steps, the SO of catalyst2/SO3Conversion ratio is higher.In a word, the fresh denitration catalyst that prepared by the present invention
Catalyst after agent and processing with the conditions of when evaluating, and the escaping of ammonia is lower than other comparative examples, with good resistance cigarette
Effect containing heavy metal deposition in gas.
Beneficial effects of the present invention：
(1) using the method for mixing in situ, titanium atom and molybdenum atom is mixed in atomic level, cause follow-up co-precipitation
During the crystal that produces, lattice defect is more, and mixed-metal oxides particle diameter is small and homogeneous, bigger than surface, improves simultaneously
Turn brilliant temperature of titanium dioxide crystal, beneficial to the performance of catalytic activity；
(2) vanadium source is added when titanium dioxide-molybdenum trioxide co-precipitation material is not calcined, in titanium-tungsten particle surface penetration
It is deeper, connect closer, disperse evenly, fired rear catalyst activity is more preferably；
(3) using phosphorous oxides in the deposition of catalyst microparticle surfaces, increase catalyst surface acidity improves catalyst
Low temperature active.
(4) the vanadium molybdenum titanium phosphorus powder material prepared entered after roasting, and covered one layer of molybdenum trioxide on its surface, while plus
Enter pore-creating auxiliary agent, also possessed nanometer level microporous while making catalyst particle surface that there are more molybdenum oxides to adhere to, both can be with
Heavy metals of flue gases oxide is resisted in its surface nonuniform deposition, high catalyst performance can be ensured again.
(5) gap of titanium dioxide matrix particle is filled using nanometer silicon dioxide particle, increases the cause of catalyst matrix
Density, and then increase the intensity of calcined catalyst.
(6) using pore creating material, binding agent, the auxiliary agent such as glass fibre by catalyst preparation into excellent activity and intensity
Cellular catalyst, beneficial to its modularization assembling and the long-period stable operation on industrial denitrification apparatus.
(7) non-calcined catalyst idiosome is impregnated using silicon source precursor solution, calcined catalyst surface can be attached
One layer of porous, inorganic silicon, the water repelling property of catalyst can be increased, while sulfur dioxide in flue gas contact can also be hindered to urge
The activated centre of agent layer, reduces SO2Oxygenation efficiency.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. one kind reduction light-off temperature and SO2The preparation method of oxygenation efficiency honeycomb type flue gas denitration catalyst, the catalyst preparation side
Method comprises the following steps：
(1) titanium source presoma is dissolved in acid and forms solution；
(2) molybdenum source presoma and phosphorus source precursor are dissolved to form solution, and are well mixed with the solution of (1)；
(3) well mixed rear solution ph, to 7~12, is precipitated obtained by regulating step (2), and filter cake is washed to obtain in filtering；
(4) deionized water is added in filter cake obtained by step (3), is tuned into pulpous state, added vanadium source precursor solution, be well mixed
Afterwards, directly it is dried, is calcined, grinds to form powder；
(5) extrusion aid, solution, the pore creating material of the formation of molybdenum source presoma are added in powder obtained by step (4), is added water while stirring
With into paste, and pH value is adjusted to 7~12；
(6) nano silicon, glass fibre, binding agent are added in lotion obtained by step (5), stir mixing, utilized
Extruder extrudes honeycomb fashion idiosome；
(7) gained idiosome in step (6) dried, be then placed in dipping in silicon source precursor solution, then be calcined, got product.
2. the preparation method of denitrating catalyst according to claim 1, it is characterised in that the molybdenum source presoma is with MoO3
Meter, titanium source presoma is with TiO2Meter, the quality of well mixed rear Molybdenum in Solution source presoma and titanium source presoma obtained by step (2)
Than for 2.0~5.0:100；Molybdenum source presoma used and titanium source forerunner body mass ratio used in step (1) are 0.5 in step (5)
~2:100；Phosphorus source presoma is with P in the step (2)2O5Meter, titanium source presoma is with TiO2Meter, step (2) gained is well mixed
The mass ratio of phosphorus source presoma and titanium source presoma is 0.1~1.5 in solution afterwards:100.
3. the preparation method of denitrating catalyst according to claim 1, it is characterised in that pore creating material be polyethylene glycol oxide,
One or more in polymethyl methacrylate, sesbania powder.
4. the preparation method of denitrating catalyst according to claim 1, it is characterised in that vanadium source presoma is with V2O5
Meter, the titanium source presoma is with TiO2The mass ratio of meter, vanadium source presoma consumption and titanium source presoma consumption is 0.3~2.0:
100。
5. the preparation method of denitrating catalyst according to claim 1, it is characterised in that nanometer two in the step (6)
Silica, glass fibre, binding agent addition with TiO2The mass ratio of the titanium source presoma of meter is respectively 0.1~2.5:100,
1~8:100,0.1~1.0:100.
6. the preparation method of denitrating catalyst according to claim 1, it is characterised in that in the step (7) before silicon source
It is 5~20s to drive body dip time.
7. the preparation method of denitrating catalyst according to claim 1, it is characterised in that the step (4) and step (7)
Middle sintering temperature is 400~650 DEG C, and roasting time is 4~40h.
8. the preparation method of denitrating catalyst according to claim 1, it is characterised in that extrusion aid in the step (5)
Addition with TiO2The mass ratio of the titanium source presoma of meter is respectively 0.01~1.0:100.
9. the preparation method of denitrating catalyst according to claim 1, it is characterised in that pore creating material in the step (5)
Addition with TiO2The mass ratio of the titanium source presoma of meter is respectively 0.01~1.0:100.
10. reduction light-off temperature and SO described in a kind of any one of claim 1 to 92Oxygenation efficiency honeycomb type flue gas denitration catalyst
Preparation method prepare catalyst, the catalyst be vanadium system O composite metallic oxide catalyst, it is characterised in that the catalyst
For 40~120m of specific surface area2/ g, by weight percentage, wherein be 80~90% containing titanium dioxide, containing molybdenum trioxide 1~
10%, containing vanadic anhydride 0.3~3%, containing phosphorus pentoxide 0.1%~2%, containing silica 0.1%~5%, containing three oxygen
Change two aluminium 0.1%~10%.
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| CN112275294A (en) * | 2020-11-05 | 2021-01-29 | 中国科学院兰州化学物理研究所 | Honeycomb type ultralow-temperature denitration catalyst and preparation method thereof |
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